Fluorescent monomers and tagged treatment polymers containing same for use in industrial water systems

ABSTRACT

The present disclosure relates to methods and compositions for making and using fluorescent monomers which are synthesized by reacting a substituted or non-substituted benzoxanthene anhydride with an amine and with a moiety containing a polymerizable group. Such monomers are useful for the preparation of tagged treatment polymers. Such tagged treatment polymers are useful as scale inhibitors in industrial water systems.

TECHNICAL FIELD

The present invention relates generally to fluorescent monomers. Inanother aspect, this invention relates to tagged treatment polymers thatcontain these fluorescent monomers. In a further aspect, this inventionrelates to the use of tagged treatment polymers containing fluorescentmonomer(s) therein in industrial water systems.

BACKGROUND

In many industrial water systems that employ polymers as water treatmentagents it may be desirable to tag or mark such polymers to facilitatemonitoring thereof. By the term “monitoring” is meant herein any type oftracing or tracking to determine the location or route of the polymers,and any type of determination of the concentration or amount of thepolymer at any given site, including singular or intermittent orcontinuous monitoring. For instance, it may be desirable to monitorwater treatment polymers in water systems, or to monitor polymers thatmay be present in waste fluids before disposal, or to monitor thepolymer used in fluids for down-hole oil well applications, or tomonitor polymers that may be present in fluids used to wash amanufactured product.

As seen from the above list of possible applications of polymermonitoring, the purpose of such monitoring may be to trace or track ordetermine the level of the polymer itself, or to trace or track ordetermine the level of some substance in association with the polymer,or to determine some property of the polymer or substance in associationwith the polymer, for instance its leachability.

There are many industrial water systems. Because water resources arebecoming limited and efficient utilization of water is required, variousmethods have been adopted to reduce the amount of water used in allindustrial water systems. As the methods for reducing the amount ofwater are put into practice, unfavorable events can occur. Theseunfavorable events occur because the quality of the water in the systemis progressively deteriorated. These unfavorable events can include theformation of scale.

To prevent or minimize unfavorable events, various kinds of treatmentagents for treatment of water systems have been used. It has been foundthat organic substances, including certain types of treatment polymers,are effective for preventing formation of scale. These certain types oftreatment polymers are known to persons of ordinary skill in the art ofindustrial water treatment and are widely used by themselves or as oneof many possible components in scale inhibition products.

When a treatment polymer is used for preventing formation of scale theconcentration of the treatment polymer in the water system is theimportant factor so that the treatment polymer performs the desiredfunction with good efficiency. For example, a treatment polymer added toa cooling water system can be consumed by many causes. With consumption,the amount of the treatment polymer dissolved in the cooling water doesnot remain the same as the amount added to the cooling water. Therefore,it is important for the optimum operation of an industrial water systemthat practical methods are known to determine the concentration oftreatment polymers in the water of the industrial water system.

In general practice, the amount of the treatment polymer added to thewater in an industrial water system can be measured using variousanalytical methods. The use of an inert fluorescent tracer or massbalance measurement method as described in U.S. Pat. Nos. 4,783,314;4,992,380; and 5,171,450, hereby incorporated by reference; to performthis analysis is known in the art.

In the inert fluorescent tracer method, an inert fluorescent tracer isadded to an industrial water system, with the amount of inertfluorescent tracer added being proportional to the amount of thetreatment polymer added. By using a fluorometer to measure thefluorescent signal of the inert fluorescent tracer, the amount of theinert fluorescent tracer can be determined by using a calibration curveto relate the amount of fluorescent signal detected to the amount of theinert fluorescent tracer present. Because the inert fluorescent tracerand the treatment polymer are added to the industrial water system inknown proportions, by knowing the amount of inert fluorescent tracerpresent it also means that the amount of treatment polymer present isknown.

The inert fluorescent tracer method can be conducted on-line and in realtime so that any changes in the amount of treatment polymer being addedto the system can be made immediately. As a complement to the use of aninert tracer system, it has been found that treatment polymers that areused as components of scale inhibitors in industrial water systems couldbe monitored if tagged with a fluorescent monomer. The amount offluorescent monomer incorporated into the tagged treatment polymer mustbe enough so that the fluorescence of the tagged treatment polymer canbe adequately measured; however, it must not be so much that theperformance of the tagged treatment polymer as a treatment agent for thewater is decreased. Because the concentration of the tagged treatmentpolymer itself can be determined using a fluorometer, it is now possibleto measure consumption of the tagged treatment polymer directly. It isimportant to be able to measure consumption directly because consumptionof a treatment polymer usually indicates that a non-desired event, suchas scaling, is occurring. Thus, by being able to measure consumption ofthe tagged treatment polymer, there can be achieved an on-line, realtime, in-situ measurement of scaling activity in the cooling system.

There are a number of florescence measuring processes and tagged polymerprocess known in the art. Some examples are described in U.S. Pat. Nos.:5,986,030, 6,312,644, 6,645,428, 7,148,351, 7,601,789, 7,875,720,6,358,746, 3,888,863, 3,310,564, 3,845,075, and 4,377,703, InternationalPublished Patent Applications: WO 2011/036075 A1 and WO2008/001036 A2,Canadian Patent Document CA 884330 A, United Kingdom Patent Documents:GB 1,378,880, GB 1,518,855, GB 1,392,253, GB 1,384,821, GB 1,095,784, GB1,345,176 and scientific papers: Synthesis of a NovelOxoxanthenoisoquinoline via a Palladium-Catalysed Cross-CouplingReaction; as a Fluorophore, by Mark P Prickett et al., TetrahedronLetters, Vol. 41, Issue 16, pp. 2987-2990 (2000) and Benzo[k, l],Xanthene-3,4-Dicarboximides andBenzimidazoxanthenoisoquinolinones—Yellow and Orange Dyes forSynthetic-Polymer Fibres, by A T Peters et al., Journal of the Societyof Dyers and Colourists, Vol. 105, Issue 1, pp. 29-35 (1989). However,there are few viable tagged treatment polymers for use as treatmentpolymers in industrial water systems. Therefore, it is desirable toproduce additional tagged treatment polymers that have a fluorescentsignal so that a fluorometer can be used to measure the fluorescentsignal of the tagged treatment polymer and determine the concentrationof tagged treatment polymer currently present in the industrial watersystem from that information.

It is known that tagging of polymers is difficult to accomplish becauseof the difficulty in chemically combining fluorescent moieties withnon-fluorescent polymers. Therefore, in order to synthesize taggedtreatment polymers it is also desirable to produce fluorescent monomersthat are readily polymerized to form tagged treatment polymers.

Thus it is clear that there is definite utility in novel methods andcompositions for making and using tagged treatment polymers. The artdescribed in this section is not intended to constitute an admissionthat any patent, publication or other information referred to herein is“Prior Art” with respect to this invention, unless specificallydesignated as such. In addition, this section should not be construed tomean that a search has been made or that no other pertinent informationas defined in 37 CFR § 1.56(a) exists.

BRIEF SUMMARY

At least one embodiment of the invention is directed towards novelmonomers, novel polymers made from those monomers, and novel methods oftheir use as tagged polymers.

At least one embodiment of the invention is directed towards a method ofmaintaining a desired amount of tagged treatment polymer in anindustrial water system comprising the steps of: a) adding an inerttracer and a tagged treatment polymer to the water of an industrialwater system, such that a desired concentration of said tagged treatmentpolymer is present in said water, b) using a fluorometer to detect thefluorescent signals of said inert tracer and said tagged treatmentpolymer, c) converting the fluorescent signals of said inert tracer andsaid tagged treatment polymer to the concentration of said inert tracerand said tagged treatment polymer, and d) adjusting the concentration ofsaid tagged treatment polymer according to what the desiredconcentration is for said tagged treatment polymer in said industrialwater system.

The tagged treatment polymer may be selected from the group consistingof: G_(a)Q_(j)W_(t), G_(a) Q_(v) W_(f) S_(c), and any combinationthereof. G, Q, W and S may all be monomeric units (a polymer is a chainof chemically bonded monomeric units) making up a backbone of a polymerchain. G is the tag and Q, W, and S are other monomeric units. Thedistribution of G, Q, W and S along the polymer chain are in randomorder and in relative amounts of a, j, t, v, f, and c. For polymer G_(a)Q_(v) W_(f) S_(c) a may be from about 0.001 to about 10.00 mole percent;v may be from about 0 to about 97.999 mole percent; f may be from about1 to about 97.999 mole percent; c may be from about 1 to about 40 molepercent; and a+v+f+c=100. For polymer G_(a)Q_(j)W_(t) a may be fromabout 0.001 to about 10.0 mole percent; j may be from about 0 to about99.999 mole percent; t may be from about 0 to about 99.999 mole percent;and a+j+t=100.

The polymer may be a tripolymer, a terpolymer, or any other sort ofcopolymer made up of multiple kinds of monomeric units.

G may be selected from the group consisting of Formula I, Formula II,

In Formula I: Y may be one or more of the following: H, F, Cl, Br, NO₂,CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its salts, SO₂NH₂ orSO₂NR₂; Z may be one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂⁺, NOH, O, S, SO, or SO₂; R₁ and R₂ may be alkyl; R₃ may be selectedfrom the group consisting of allyl, 2-hydroxy-3-allyloxy-propyl, vinylbenzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl and2-methacryloxyethyl. A may be selected from the group consisting ofalkyl, alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with theproviso that when A is nonexistent, B is nitrogen (N) and B is bondeddirectly to the imide nitrogen. B may be sulfur or nitrogen with theproviso that when B is sulfur only one of R₁ or R₂ is present. X may bean anionic counter ion.

In Formula II: Y may be one or more of the following: H, F, Cl, Br, NO₂,CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its salts, SO₂NH₂ orSO₂NR₂; Z may be one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂⁺, NOH, O, S, SO, or SO₂; A may be selected from the group consisting ofalkyl, alkyloxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, aryl ornonexistent; R₄ is selected from the group consisting of allyl, acryl,methacryl, 2-hydroxy-3-allyloxy-propyl, vinyl benzyl, 2-acryloxyethyland 2-methacryloxyethyl.

Q may be selected from the group consisting of acrylic acid and saltsthereof, methacrylic acid and salts thereof, maleic acid and saltsthereof, maleic anhydride, acrylamide, crotonic acid,acrylamidomethylpropane sulfonic acid and salts thereof; and Q cannot bethe same as W.

S may be selected from the group consisting of sulfomethylacrylamide andsulfoethylacrylamide.

W may be selected from the group consisting of: acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, diallylamine, acid salts of diallylamine, triallylamine,acid salts of triallylamine, ethylene glycol dimethacrylate,hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidylmethacrylate, acrylamidomethylpropane sulfonic acid and the sodium saltthereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone.

DETAILED DESCRIPTION

The following definitions are provided to determine how terms used inthis application, and in particular how the claims, are to be construed.The organization of the definitions is for convenience only and is notintended to limit any of the definitions to any particular category.“Aldrich” means Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wis.53201 USA, Telephone Numbers (414) 273-3850 and (800) 558-9160;

“Aliphatic Amine” refers to amines in which the amine group is attachedto a saturated carbon atom;

“Alkoxy” means a moiety of the formula RO—, where R is alkyl;

“Alkoxylalkyl” means a moiety of the formula R—O—R₁, where R and R₁ arealkyl;

“Alkylamidoalkyl” means a moiety of the formula R—C(O)NH—R₁—, where Rand R₁ are alkyl;

“Alkylamino” means a moiety of the formula R—NH—, where R is alkyl;

“Alkyl”, whenever it is used, means a fully saturated hydrocarbon moietywith from 1 to 10 carbon atoms;

“Allyl” means a moiety of the formula —CH₂CH═CH₂;

“Anionic Counter Ion” means an organic or inorganic ion that bears anegative charge to counterbalance the positive charge present on themonomer. Examples include, but are not limited to chloride, sulfate,acetate, methylsulfate, hydroxide and bromide;

“Aryl” means a moiety of the formula Ar—, where Ar is an aromatic unit;

“Benzoxanthene” means a moiety of the formula:

“Branching Agent” means a “Cross-Linking Agent” that is administered ata low level (less than 0.05 weight percent based on the weight of thepolymer). It is understood that Branching Agents are added to form“branches” not cross-links;

“Carboxylate” means a moiety of —C(O)OM, where M is H, Na or anothercationic counter ion;

“Chain Transfer Agent” means any molecule, used in free-radicalpolymerization, which will react with a polymer radical forming a deadpolymer and a new radical. Representative Chain Transfer Agents arelisted by K. C. Berger and G. Brandrup, “Transfer Constants to Monomer,Polymer, Catalyst, Solvent, and Additive in Free RadicalPolymerization,” Section II, pp. 81-151, in “Polymer Handbook, ” editedby J. Brandrup and E. H. Immergut, 3d edition, 1989, John Wiley & Sons,New York.

“Cross-Linking Agent” means a composition of matter which chemicallylinks two distinct polymer chains, such as a composition that links anethylenically unsaturated monomer either containing at least two sitesof ethylenic unsaturation or containing one site of ethylenicunsaturation and one site of a reactive group such as an epoxide or analdehyde. A Cross-Linking Agent may be added to branch or increase themolecular weight of the tagged treatment polymer of this invention.Representative Cross-Linking Agents include N,N-methylenebisacrylamide,N,N-methylenebismethacrylamide, polyethylene glycol diacrylate, ethyleneglycol dimethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, polyethylene glycol dimethacrylate, polypropyleneglycol dimethacrylate, N-vinyl acrylamide, divinyl benzene, triallylammonium salts, N-methyl allylacrylamide, glycidyl acrylate, acrolein,methylolacrylamide, glyoxal, epichlorohydrin, and the like. Thecrosslinker may be added at from about 0.0001 to about 10, preferablyfrom about 0.0001 to about 0.2 weight percent based on the weight of thepolymer;

“Dialkylamino” means a moiety of the formula R₂₁—N—R₂₂, where R₂₁ andR₂₂ are alkyl;

“Halogen” means a moiety selected from the group consisting of F, Cl,Br, and I;

“HLB” means the hydrophillic-lipophillic balance of a composition whichis a measure of the degree to which it is hydrophilic or lipophilic, itcan be determined by the equation:HLB=20*Mh/Min which Mh is the molecular mass of the hydrophilic portion of theMolecule, and M is the molecular mass of the whole molecule, giving aresult on a scale of 0 to 20. An HLB value of 0 corresponds to acompletely lipidphilic/hydrophobic molecule, and a value of 20corresponds to a completely hydrophilic/lipidphilic molecule. HLB valuesare characterized as:

-   -   HLB<10: Lipid soluble (water insoluble)    -   HLB>10: Water soluble (lipid insoluble)    -   HLB from 4 to 8 indicates an anti-foaming agent    -   HLB from 7 to 11 indicates a W/O (water in oil) emulsifier    -   HLB from 12 to 16 indicates O/W (oil in water) emulsifier    -   HLB from 11 to 14 indicates a wetting agent    -   HLB from 12 to 15 indicates a detergent    -   HLB of 16 to 20 indicates a solubiliser or hydrotrope.

“Hydroxyalkyl” means a moiety where an —OH group is attached to an alkylgroup;

“Spectrometry” and “Spectroscopy” means the process of analyzing theinteraction between a sample of matter and electromagnetic radiation todetermine one or more physical properties of the sample of matter. Formsof electromagnetic radiation used include but are not limited to one ormore of microwave, terawave, infrared, near infrared, visible,ultraviolet, x-ray, radiation. The analysis includes measurements of oneor more of the radiation's absorption, emission, fluorescence,colorometrics, color changes, reflection, scattering, impedance,refraction, and resonance by the sample of matter.

“Substituted Aliphatic Amine” means amines in which the amine group isattached to a saturated carbon of an organic molecule which may bearfunctional groups such as hydroxyl, carboxyl, etc.;

“Surfactant” is a broad term which includes anionic, nonionic, cationic,and zwitterionic surfactants. Enabling descriptions of surfactants arestated in Kirk-Othmer, Encyclopedia of Chemical Technology, ThirdEdition, volume 8, pages 900-912, and in McCutcheon's Emulsifiers andDetergents, both of which are incorporated herein by reference.

“Vinyl” means a moiety which has a carbon-carbon double bond;

“Vinylbenzyl” means a moiety of the formula;

“Vinylbenzyloxy” means a moiety of the formula:

“Water Soluble” means materials that are soluble in water to at least3%, by weight, at 25 degrees C.

In the event that the above definitions or a description statedelsewhere in this application is inconsistent with a meaning (explicitor implicit) which is commonly used, in a dictionary, or stated in asource incorporated by reference into this application, the applicationand the claim terms in particular are understood to be construedaccording to the definition or description in this application, and notaccording to the common definition, dictionary definition, or thedefinition that was incorporated by reference. In light of the above, inthe event that a term can only be understood if it is construed by adictionary, if the term is defined by the Kirk-Othmer Encyclopedia ofChemical Technology, 5th Edition, (2005), (Published by Wiley, John &Sons, Inc.) this definition shall control how the term is to be definedin the claims.

In at least one embodiment of the invention one or more fluorescentmonomers is useful in the preparation of tagged treatment polymerscontaining same, with said tagged treatment polymers in turn being ableto provide a means for achieving better monitoring in industrial watersystems.

In at least one embodiment a fluorophore is used using a benzoxanthenemoiety. It has an advantageous spectral profile with respect to standardbackground fluorescence interference, leading to improved signaldetection. It can also be incorporated within a water-soluble polymer inlower loading levels than prior art tagging materials.

While benzoxanthenes have been used as fluorescent dyes for textiles andHDPE polymers, the prior art does not contemplate the use of thebenzoxanthene fluorophore as a fluorescent tag for water solublepolymers. Moreover these tags display a number of unexpected results.The benzoxanthene fluorophore has greater intensity and better halogenstability than current tags. In addition, it has better stability inlight compared to the current tagged polymer via fluorescence. Asulfonated benzoxanthene structure has improved water solubility,whereas the unsulfonated benzoxanthene is oil soluble. This also meansthat the benzoxanthene can be incorporated within a water-solublepolymer in lower loading levels than current tags. The benzoxanthenefluorophore has an advantageous spectral profile with respect tostandard background fluorescence in cooling tower waters.

An advantage of the fluorescent monomers of this invention is that intheir use in the formation of a tagged treatment polymer, thefluorescent monomer is not significantly affected by other structures inthe polymer or by other ingredients in the system. Thus, the polymersare stable in the presence of oxidizing biocides containing chlorine andor bromine, available from Nalco an Ecolab Company, 1601 West Diehl Rd,Naperville, Ill. 60563.

A further advantage of the tagged treatment polymers of this inventionis that the spectral properties, i.e. both excitation and emission ofthe polymers are in the near visible wavelength region (>390 nm), thusallowing the use of solid state instrumentation and potentially minimizeinterferences that generally occur in the UV wavelength region.

In at least one embodiment the fluorescent monomer is selected from thegroup consisting of a compound of: Formula I, Formula II, and anycombination thereof.

In Formula I: Y is one or more of the following: H, F, Cl, Br, NO₂, CO₂Hand its salts, PO₃H₂ and it salts, SO₃H and its salts, SO₂NH₂ or SO₂NR₂;Z is one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂ ⁺, NOH, O,S, SO, or SO₂; R₁ and R₂ are alkyl; R₃ is selected from the groupconsisting of allyl, 2-hydroxy-3-allyloxy-propyl, vinyl benzyl,3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl and2-methacryloxyethyl. A is selected from the group consisting of alkyl,alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with the provisothat when A is nonexistent, B is nitrogen (N) and B is bonded directlyto the imide nitrogen. B is sulfur or nitrogen with the proviso thatwhen B is sulfur only one of R₁ or R₂ is present; X is an anioniccounter ion;

In Formula II: Y is one or more of the following: H, F, Cl, Br, NO₂,CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its salts, SO₂NH₂ orSO₂NR₂; Z is one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂ ⁺,NOH, O, S, SO, or SO₂; A is selected from the group consisting of alkyl,alkyloxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, aryl ornonexistent; R₄ is selected from the group consisting of allyl, acryl,methacryl, 2-hydroxy-3-allyloxy-propyl, vinyl benzyl, 2-acryloxyethyland 2-methacryloxyethyl.

In at least one embodiment, Y is sulfonic acid or hydrogen; Z is O orSO₂; R₁ and R₂ are alkyl; R₃ is 2-hydroxy-3-allyloxy-propyl, allyl,vinyl benzyl, or 3-methacrylamidopropyl; B is nitrogen; A is an alkylgroup of 1 to 10 carbon atoms; and X is an anionic counter ion.

Acceptable names for Formula I monomeric units are:

Sulfonated-N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)xanthene-3,4-dicarboxylic imide, 2-Hydroxy-3-Allyloxypropyl Quat andSulfonated-N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)sulfonylxanthene-3,4-dicarboxylic imide, 2-Hydroxy-3-AllyloxypropylQuat.

Monomers of Formula I can be synthesized by reacting a benzoxanthenedicarboxylic anhydride or a sulfonated benzoxanthene dicarboxylicanhydride with a primary amine. The amine can be aliphatic, vinyl,substituted aliphatic or hydrazine. Suitable solvents include water,glacial acetic acid or any solvent system suitable for forming thearomatic fluorescent core. Materials required for these syntheses arecommercially available and can be obtained from Aldrich. Polymerizablemoieties can be introduced through substitution on the aromatic ring orduring quaterization or imidization.

“Tagging” the polymer through the use of the fluorescent monomers ofthis invention is achieved by synthesizing the polymer in the presenceof the fluorescent monomer.

In at least one embodiment, Formula I and, or Formula II is used tosynthesize tagged treatment polymers of formulas: (1) G_(a)Q_(j)W_(t)and (2) G_(a) Q_(v) W_(f) S_(c), wherein:For G_(a)Q_(j)W_(t):  (1)

G is selected from the group consisting of Formula I and/or Formula II,as previously defined; Q is selected from the group consisting ofacrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, acrylamidomethylpropane sulfonic acid and salts thereof;

W is selected from the group consisting of:

acrylic acid and salts thereof, methacrylic acid and salts thereof,itaconic acid and salts thereof, maleic acid and salts thereof, maleicanhydride, crotonic acid and salts thereof, acrylamide, methacrylamide,vinyl sulfonic acid, styrene sulfonate, N-tertbutylacrylamide,N-isopropylacrylamide, butoxymethylacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl chloridequaternary salts, dimethylaminoethyl acrylate benzyl chloride quaternarysalts, dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, diallylamine, acid salts of diallylamine, triallylamine,acid salts of triallylamine, ethylene glycol dimethacrylate,hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidylmethacrylate, acrylamidomethylpropane sulfonic acid and the sodium saltthereof, vinyl alcohol, vinyl acetate, and N-vinylpyrrolidone;

with the proviso that Q and W cannot both be the same;

a is from about 0.001 to about 10.0 mole percent;

j is from about 0 to about 99.999 mole percent;

t is from about 0 to about 99.999 mole percent; and

a+j+t=100.For G_(a) Q_(v) W_(f) S_(c):  (2)

G is as previously defined; Q is as previously defined; W is aspreviously defined, with the proviso that Q and W cannot both be thesame;

S is selected from the group consisting of sulfomethylacrylamide andsulfoethylacrylamide;

a is from about 0.001 to about 10.00 mole percent;

v is from about 0 to about 97.999 mole percent;

f is from about 1 to about 97.999 mole percent;

c is from about 1 to about 40 mole percent; and

a+v+f+c=100.

These tagged treatment polymers can be synthesized by following theprocedure for conventional free radical polymerization in an aqueousmedium. They can be made by water-in-oil polymerization methods ordispersion polymerization methods or solution polymerization methods.For those tagged treatment polymers containing a sulfomethylated orsulfoethylated acrylamide, the polymers are first created with anacrylamide moiety, and then the acrylamide groups are sulfomethylatedusing a suitable “sulfo” reagent such as formaldehyde and sodiummetabisulfite.

Procedure for Synthesizing Water-In-Oil Emulsion Polymers

The preparation of high molecular weight water-in-oil emulsion polymershas been described in the following references: U.S. Pat. No. 2,982,749assigned to The Dow Chemical Company; U.S. Pat. No. 3,284,393 assignedto The Dow Chemical Company; U.S. Pat. No. 3,734,873 assigned to NalcoChemical Company; “Mechanism, Kinetics and Modeling of theInverse-Microsuspension Homopolymerization of Acrylamide,” by Hundeler,D., Hamielec, A. and Baade, W., Polymer (1989), 30(1), 127-42; and“Mechanism, Kinetics and Modeling of Inverse-MicrosuspensionPolymerization: 2. Copolymerization of Acrylamide with QuaternaryAmmonium Cationic Monomers,” by D. Hunkeler and A. E. Hamielec; Polymer(1991), 32(14), 2626-40.

A general procedure for the manufacture of water-in-oil emulsion taggedtreatment polymers is provided to illustrate the preparation of thesetagged treatment polymers using fluorescent monomers. The types andquantities of specific components in the formula (monomers, initiators,Chain Transfer Agents, for example) will vary depending upon the type ofpolymer (cationic, anionic, nonionic) that is being synthesized.

An aqueous phase is prepared by mixing together in water one or morewater soluble monomers, and different polymerization additives such asinorganic salts, chelants, pH buffers, Chain Transfer Agents andBranching or Cross-Linking Agents. In order to synthesize the taggedtreatment polymers of the instant claimed invention, a monomer offormula Formula I and, or Formula II is included in the aqueous phase atthe desired level.

An organic phase is prepared by mixing together an inert hydrocarbonliquid with one or more oil soluble surfactants. The surfactant mixtureshould have a low HLB, to ensure the formation of an oil continuousemulsion. Appropriate surfactants for water-in-oil emulsionpolymerizations, which are commercially available, are compiled in theNorth American Edition of McCutcheon's Emulsifiers & Detergents. The oilphase may need to be heated to ensure the formation of a homogeneous oilsolution.

The oil phase is charged into a reactor equipped with a mixer, athermocouple, a nitrogen purge tube, and a condenser. Adding the aqueousphase to the reactor containing the oil phase with vigorous stirringforms an emulsion. The resulting emulsion is heated to the desiredtemperature, purged with nitrogen, and a free-radical initiator isadded. The reaction mixture is stirred for several hours under anitrogen atmosphere at the desired temperature. Upon completion of thereaction, the water-in-oil emulsion polymer is cooled to roomtemperature, where any desired post-polymerization additives, such asantioxidants, or a high HLB surfactant (as described in U.S. Pat. No.3,734,873) may be added.

The resulting emulsion polymer is a free-flowing liquid. An aqueoussolution of the water-in-oil emulsion polymer can be generated by addinga desired amount of the emulsion polymer to water with vigorous mixingin the presence of a high-HLB surfactant (as described in U.S. Pat. No.3,734,873).

Procedure for Synthesizing Dispersion Polymers

The preparation of dispersion polymers has been described in thefollowing references: U.S. Pat. No. 4,929,655, assigned to HymoCorporation; U.S. Pat. No. 5,006,590, assigned to Hymo Corporation; U.S.Pat. No. 5,597,859, assigned to Nalco Chemical Company; European Patent657,478; U.S. Pat. No. 5,597,858, assigned to Nalco Chemical Company andEuropean Patent 630,909.

A general procedure for the manufacture of dispersion tagged treatmentpolymers is provided in the following text in order to illustrate thepreparation of dispersion tagged treatment polymers comprising thefluorescent monomers described herein. The types and quantities ofspecific components in the formula (salts and stabilizer polymers, forexample) will vary depending upon the type of polymer (cationic,anionic, nonionic) that is being synthesized.

An aqueous solution containing one or more inorganic salts, one or morewater-soluble monomers, any polymerization additives such as chelants,pH buffers, Chain Transfer Agents, Branching or Cross-Linking Agents anda water-soluble stabilizer polymer is charged to a reactor equipped witha mixer, a thermocouple, a nitrogen purging tube, and a water condenser.The monomer solution is mixed vigorously, heated to the desiredtemperature, and then a water-soluble initiator is added. The solutionis purged with nitrogen while maintaining temperature and mixing forseveral hours. After this time, the products are cooled to roomtemperature, and any post-polymerization additives are charged to thereactor. Water continuous dispersions of water-soluble polymers are freeflowing liquids with product viscosities generally 100-10,000 cP,measured at low shear. Thus, in order to prepare tagged polymers asdispersions, a monomer of formula Formula I and, or Formula II isincluded in the reaction mixture at the desired level.

Procedure for Synthesizing Solution Polymers

A general procedure for the manufacture of solution polymers is providedto illustrate the preparation of the solution tagged treatment polymerscomprising the fluorescent monomers described herein. One typicalprocess is described as follows: One or more monomers are added to avessel followed by neutralization with a suitable base. The fluorescentmonomer can then be added to this monomer solution after neutralizationor alternatively, to the reaction vessel. A determined amount of wateris then added to the reaction vessel, which is then heated and purged.Polymerization catalysts may also be added to the vessel initially orfed in gradually during the course of the reaction. Water solublepolymerization initiators such as any azo or redox initiator orcombination thereof are added along with the monomer solution to thereaction mixture in separate feeds over the same amount of time, usually2 to 6 hours. The reaction temperature is maintained at about 60-70° C.Additional initiator may be used after addition is complete to reduceresidual monomer levels.

The amount of fluorescent monomer that is used should be an amountsufficient to allow the tagged treatment polymer to be detected in theaqueous environment that it is used. The minimum amount of fluorescentmoiety that can be used is that amount which gives a signal-to-noiseratio (S/N) of 3 at the desired tagged treatment polymer dosage. Thesignal-to-noise ratio is that value where the magnitude of thetransduced signal (including but not limited to electronic and opticalsignals) due to the presence of a target analytic in a measurementdevice is greater than or equal to a level three (3) times the magnitudeof a transduced signal where the analyte (species) of interest is notpresent in the measurement device.

The amount of fluorescent monomer in the tagged treatment polymers is inthe range of from about 0.001 mole percent to about 10 mole percent,preferably from about 0.01 mole percent to about 0.4 mole percent, andmost preferably from about 0.05 mole percent to about 0.35 mole percent.For purposes of this patent application, mole percent of all monomers inthe tagged treatment polymer is calculated based on weight percent. Forpurposes of this patent application, the subscripts a, j, t, v, f and crefer to the mole percent of each monomer component of the taggedtreatment polymers.

The remainder of the tagged treatment polymer can have one, two or threeadditional monomers in it.

All molecular weights in this patent application are weight averagemolecular weights measured by gel permeation chromatography (GPC)calculated from both refractive index and fluorescent detector tracesusing polystyrene sulfonate (PSS) molecular weight standards. Taggedtreatment polymers that have a wide range of molecular weights can beprepared by using the procedures described previously by those skilledin the art.

The molecular weights of the instant claimed tagged treatment polymersare from about 500 atomic mass units (hereinafter “a.m.u.”) to about10,000,000 a.m.u. Preferably the molecular weights are from about 2000a.m.u. to about 500,000 a.m.u. Most preferably, the molecular weightsare from about 5000 a.m.u. to about 40,000 a.m.u.

Preferred tagged polymers are made via solution polymerizationtechniques and have a molecular weight from about 5,000 a.m.u. to about40,000 a.m.u.

Preferred tagged treatment polymers are where said fluorescent monomeris selected from the group consisting of:

Sulfonated-N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)xanthene-3,4-dicarboxylic imide, 2-Hydroxy-3-Allyloxypropyl Quat(S-NDMAPBXA-DCI-HAPQ)

The more preferred polymers are where G is Formula I as previouslydefined; Q, if present in the polymer, is selected from the groupconsisting of acrylamide and acrylic acid; W, if present in the polymer,is selected from the group consisting of acrylamide andacrylamidomethylpropane sulfonic acid; and S, if present in the polymer,is N-sulfomethylacrylamide.

The most preferred polymers are selected from the group consisting of0.2 mole % S-NDMAPBXA-DCI-HAPQ/80.9 mole % Acrylic Acid/ 18.9 mole %Acrylamidomethylpropane sulfonic acid.

Once created the tagged treatment polymers of the instant claimedinvention can be used as scale inhibitors in industrial water systems.As these polymers are consumed performing that function, theirfluorescent signal will decrease and thus the decrease in thefluorescent signal can be used to indicate that undesired scaling istaking place.

The tagged treatment polymers containing a fluorescent monomer can beused in industrial water systems. Examples of industrial water systemsare cooling tower water systems (including open recirculating, closedand once-through systems); petroleum wells, downhole formations,geothermal wells and other oil field applications; boilers and boilerwater systems; mineral process waters including mineral washing,flotation and benefaction; paper mill digesters, paper production,washers, bleach plants and white water systems; black liquor evaporatorsin the pulp industry; gas scrubbers and air washers; continuous castingprocesses in the metallurgical industry; air conditioning andrefrigeration systems; industrial and petroleum process water; indirectcontact cooling and heating water, such as pasteurization water; waterreclamation and purification systems; membrane filtration water systems;food processing streams (meat, vegetable, sugar beets, sugar cane,grain, poultry, fruit and soybean); and waste treatment systems as wellas in clarifiers, liquid-solid applications, municipal sewage treatmentand industrial or municipal water systems.

The tagged treatment polymer comprising a fluorescent monomer may beused in the industrial water systems singly or in combination with otherpolymers, which are not tagged. The dosage rate of tagged treatmentpolymer in an industrial water system, when it is being used as a scaleinhibitor, is from about 1 to about 100 milligrams of solid componentactive per liter of water.

At least one embodiment of the invention is a process for the inhibitionof scale formation in an industrial water system which comprisesintroducing into said industrial water system a tagged treatmentpolymer, previously described, in an amount sufficient to inhibit scaleformation. The amount of the tagged treatment polymer comprising thefluorescent monomer added to an industrial water system is in the rangeof about 1.0 milligrams (mg) to about 30 milligrams of the total solidpolymer actives per liter of water in the system. This is equivalent toabout 1 part per million (ppm) to about 30 ppm.

When used in an industrial water system, the fluorescent signal of thetagged treatment polymers can be used to determine how much taggedtreatment polymer is present in the industrial water system. A least oneembodiment of the invention is:

A method for maintaining the desired amount of tagged treatment polymerin an industrial water system comprising the steps of:

-   -   i) adding to said industrial water system a tagged treatment        polymer, wherein said tagged treatment polymer is as previously        described;    -   ii) using a fluorometer to detect the fluorescent signal of said        tagged treatment polymer;    -   iii) converting the fluorescent signal of said tagged treatment        polymer to the concentration of said tagged treatment polymer;        and    -   iv) adjusting the concentration of said tagged treatment polymer        according to what the desired concentration is for said tagged        treatment polymer in said industrial water system.

At least one embodiment of the invention is a method for maintaining thedesired amount of tagged treatment polymer in an industrial water systemcomprising the steps of:

-   -   a) adding an inert tracer and a tagged treatment polymer, as        previously described, to water such that a desired concentration        of said tagged treatment polymer is present in said water;    -   b) using a fluorometer to detect the fluorescent signals of said        inert tracer and said tagged treatment polymer;    -   c) converting the fluorescent signals of said inert tracer and        said tagged treatment polymer to the concentration of said inert        tracer and said tagged treatment polymer; and    -   d) adjusting the concentration of said tagged treatment polymer        according to what the desired concentration is for said tagged        treatment polymer in the industrial water system.        Additional Embodiments    -   1. A fluorescent monomer selected from the group consisting of        compounds of the formula:

-   -   -   wherein Y is one or more of the following: H, F, Cl, Br,            NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its            salts, SO₂NH₂ or SO₂NR₂;        -   Z is one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂            ⁺, NOH, O, S, SO, or SO₂,        -   R₁ and R₂ are alkyl        -   R₃ is selected from the group consisting of allyl,            2-hydroxy-3-allyloxy-propyl, vinyl benzyl,            3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl            and 2-methacryloxyethyl.        -   A is selected from the group consisting of alkyl,            alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with            the proviso that when A is nonexistent, B is nitrogen (N)            and B is bonded directly to the imide nitrogen.        -   B is sulfur or nitrogen with the proviso that when B is            sulfur only one of R₁ or R₂ is present;        -   X is an anionic counter ion;

    -   2. A fluorescent monomer of claim 1, wherein said monomer is        sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt.

    -   3. A fluorescent monomer of claim 1, wherein said monomer is        sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt.

    -   4. A fluorescent monomer of claim 1, wherein said monomer is        sulfonated —N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt.

    -   5. A tagged treatment polymer selected from the group consisting        of:        G_(a)Q_(j)W_(t)  (1)        -   wherein G is selected from the group consisting of:

-   -   -   wherein Y is one or more of the following: H, F, Cl, Br,            NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its            salts, SO₂NH₂ or SO₂NR₂;        -   Z is one of the following: CH₂, C═O, CR₂, NH, NR, NH₂ ⁺, NR₂            ⁺, NOH, O, S, SO, or SO₂;        -   R₁ and R₂ are alkyl        -   R₃ is selected from the group consisting of allyl,            2-hydroxy-3-allyloxy-propyl, vinyl benzyl,            3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl            and 2-methacryloxyethyl.        -   A is selected from the group consisting of alkyl,            alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with            the proviso that when A is nonexistent, B is nitrogen (N)            and B is bonded directly to the imide nitrogen.        -   B is sulfur or nitrogen with the proviso that when B is            sulfur only one of R₁ or R₂ is present;        -   X is an anionic counter ion;

    -   wherein Q is selected from the group consisting of acrylic acid        and salts thereof, methacrylic acid and salts thereof, maleic        acid and salts thereof, maleic anhydride, acrylamide, crotonic        acid, acrylamidomethylpropane sulfonic acid and salts thereof;

    -   wherein W is selected from the group consisting of:        acrylic acid and salts thereof, methacrylic acid and salts        thereof, itaconic acid and salts thereof, maleic acid and salts        thereof, maleic anhydride, crotonic acid and salts thereof,        acrylamide, methacrylamide, vinyl sulfonic acid, styrene        sulfonate, N-tertbutylacrylamide, N-isopropylacrylamide,        butoxymethylacrylamide, N,N-dimethylacrylamide,        N,N-diethylacrylamide, dimethylaminoethyl acrylate methyl        chloride quaternary salts, dimethylaminoethyl acrylate benzyl        chloride quaternary salts, dimethylaminoethyl acrylate methyl        sulfate quaternary salt, dimethylaminoethyl methacrylate methyl        sulfate quaternary salt, dimethylaminoethyl acrylamide methyl        sulfate quaternary salts, dimethylaminopropyl acrylamide methyl        sulfate quaternary salts, dimethylaminopropyl methacrylamide        methyl sulfate quaternary salts, diallyldimethyl ammonium        chloride, N-vinyl formamide, dimethylamino ethyl methacrylate        acid salts (including, but not limited to, sulfuric acid and        hydrochloride acid salts), dimethylaminoethyl methacrylate        methyl chloride quaternary salt, dimethylaminoethyl methacrylate        benzyl chloride quaternary salt, methacrylamidopropyl trimethyl        ammonium chloride, acrylamidopropyl trimethyl ammonium chloride,        methylene bis acrylamide, diallylamine, acid salts of        diallylamine, triallylamine, acid salts of triallylamine,        ethylene glycol dimethacrylate, hydroxymethylacrylate,        hydroxyethylacrylate, hydroxypropylacrylate,        hydroxypropylmethacrylate, diethylene glycol dimethacrylate,        triethylene glycol dimethylacrylate, polyethylene glycol        dimethacrylate, glycidyl methacrylate, acrylamidomethylpropane        sulfonic acid and the sodium salt thereof, vinyl alcohol, vinyl        acetate, and N-vinylpyrrolidone;

    -   with the proviso that Q and W cannot both be the same;        -   wherein a is from about 0.001 to about 10.0 mole percent;        -   wherein j is from about 0 to about 99.999 mole percent;        -   wherein t is from about 0 to about 99.999 mole percent; and        -   wherein a+j+t=100;            G_(a) Q_(v) W_(f) S_(c)  (2)        -   wherein G is as previously defined;        -   wherein Q is as previously defined;        -   wherein W is as previously defined, with the proviso that Q            and W cannot both be the same;        -   wherein S is selected from the group consisting of            sulfomethylacrylamide and sulfoethylacrylamide;        -   wherein a is from about 0.001 to about 10.00 mole percent;        -   wherein v is from about 0 to about 97.999 mole percent;        -   wherein f is from about 1 to about 97.999 mole percent;        -   wherein c is from about 1 to about 40 mole percent; and        -   wherein a+v+f+c=100.

    -   6. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl)benzo (k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt

    -   7. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt.

    -   8. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt.

    -   9. A tagged treatment polymer of claim 5 wherein Q is acrylic        acid and W is acrylamide.

    -   10. A tagged treatment polymer of claim 5 wherein Q is        acrylamide, W is acrylic acid and S is N-sulfomethylacrylamide.

    -   11. A tagged treatment polymer of claim 5 wherein Q is acrylic        acid and W is acrylamidomethylpropane sulfonic acid.

    -   12. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   13. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   14. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   15. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   16. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   17. A tagged treatment polymer of claim 5 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

    -   18. A tagged treatment polymer of claim 5 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt and Q is acrylic acid.

    -   19. A process for the inhibition of scale formation in an        industrial water system which comprises introducing into said        industrial water system a tagged treatment polymer selected from        the group consisting of:        G_(a)Q_(j)W_(t)  (1)        -   wherein G is selected from the group consisting of:

-   -   -   wherein Y is one or more of the following: H, F, Cl, Br,            NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its            salts, SO₂NH₂ or SO₂NR₂;        -   Z is one of the following: CH₂, C═O, CR₂,NH, NR, NH₂ ⁺, NR₂            ⁺, NOH, O, S, SO, or SO₂;        -   R₁ and R₂ are alkyl        -   R₃ is selected from the group consisting of allyl,            2-hydroxy-3-allyloxy-propyl, vinyl benzyl,            3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl            and 2-methacryloxyethyl.        -   A is selected from the group consisting of alkyl,            alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with            the proviso that when A is nonexistent, B is nitrogen (N)            and B is bonded directly to the imide nitrogen.        -   B is sulfur or nitrogen with the proviso that when B is            sulfur only one of R₁ or R₂ is present;        -   X is an anionic counter ion;            -   wherein Q is selected from the group consisting of                acrylic acid and salts thereof, methacrylic acid and                salts thereof, maleic acid and salts thereof, maleic                anhydride, acrylamide, crotonic acid,                acrylamidomethylpropane sulfonic acid and salts thereof;            -   wherein W is selected from the group consisting of:                acrylic acid and salts thereof, methacrylic acid and                salts thereof, itaconic acid and salts thereof, maleic                acid and salts thereof, maleic anhydride, crotonic acid                and salts thereof, acrylamide, methacrylamide, vinyl                sulfonic acid, styrene sulfonate, N-tertbutylacrylamide,                N-isopropylacrylamide, butoxymethylacrylamide,                N,N-dimethylacrylamide, N,N-diethylacrylamide,                dimethylaminoethyl acrylate methyl chloride quaternary                salts, dimethylaminoethyl acrylate benzyl chloride                quaternary salts, dimethylaminoethyl acrylate methyl                sulfate quaternary salt, dimethylaminoethyl methacrylate                methyl sulfate quaternary salt, dimethylaminoethyl                acrylamide methyl sulfate quaternary salts,                dimethylaminopropyl acrylamide methyl sulfate quaternary                salts, dimethylaminopropyl methacrylamide methyl sulfate                quaternary salts, diallyldimethyl ammonium chloride,                N-vinyl formamide, dimethylamino ethyl methacrylate acid                salts (including, but not limited to, sulfuric acid and                hydrochloride acid salts), dimethylaminoethyl                methacrylate methyl chloride quaternary salt,                dimethylaminoethyl methacrylate benzyl chloride                quaternary salt, methacrylamidopropyl trimethyl ammonium                chloride, acrylamidopropyl trimethyl ammonium chloride,                methylene bis acrylamide, diallylamine, acid salts of                diallylamine, triallylamine, acid salts of                triallylamine, ethylene glycol dimethacrylate,                hydroxymethylacrylate, hydroxyethylacrylate,                hydroxypropylacrylate, hydroxypropylmethacrylate,                diethylene glycol dimethacrylate, triethylene glycol                dimethylacrylate, polyethylene glycol dimethacrylate,                glycidyl methacrylate, acrylamidomethylpropane sulfonic                acid and the sodium salt thereof, vinyl alcohol, vinyl                acetate, and N-vinylpyrrolidone;

    -   with the proviso that Q and W cannot both be the same;        -   wherein a is from about 0.001 to about 10.0 mole percent;        -   wherein j is from about 0 to about 99.999 mole percent;        -   wherein t is from about 0 to about 99.999 mole percent; and        -   wherein a+j+t=100;            G_(a) Q_(v) W_(f) S_(c)  (2)        -   wherein G is as previously defined;        -   wherein Q is as previously defined;        -   wherein W is as previously defined, with the proviso that Q            and W cannot both be the same;        -   wherein S is selected from the group consisting of            sulfomethylacrylamide and sulfoethylacrylamide;        -   wherein a is from about 0.001 to about 10.00 mole percent;        -   wherein v is from about 0 to about 97.999 mole percent;        -   wherein f is from about 1 to about 97.999 mole percent;        -   wherein c is from about 1 to about 40 mole percent; and        -   wherein a+v+f+c=100;            in an amount sufficient to inhibit scale formation.

    -   20. A tagged treatment polymer of claim 19 wherein Q is acrylic        acid and W is acrylamide.

    -   21. A tagged treatment polymer of claim 19 wherein Q is        acrylamide, W is acrylic acid and S is N-sulfomethylacrylamide.

    -   22. A tagged treatment polymer of claim 19 wherein Q is acrylic        acid and W is acrylamidomethylpropane sulfonic acid.

    -   23. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   24. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl)benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   25. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   26. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   27. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   28. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

    -   29. A tagged treatment polymer of claim 19 wherein G is        sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt and Q is acrylic acid.        -   30. A method for maintaining the desired amount of tagged            treatment polymer in an industrial water system comprising            the steps of:        -   i) adding to said industrial water system a tagged treatment            polymer, selected from a group consisting of:            G_(a)Q_(j)W_(t)  (1)        -   wherein G is selected from the group consisting of:

-   -   -   wherein Y is one or more of the following: H, F, Cl, Br,            NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its            salts, SO₂NH₂ or SO₂NR₂;        -   Z is one of the following: CH₂, C═O, CR₂,NH, NR, NH₂ ⁺, NR₂            ⁺, NOH, O, S, SO, or SO₂;        -   R₁ and R₂ are alkyl        -   R₃ is selected from the group consisting of allyl,            2-hydroxy-3-allyloxy-propyl, vinyl benzyl,            3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl            and 2-methacryloxyethyl.        -   A is selected from the group consisting of alkyl,            alkyloxyalkyl, alkylamidoalkyl, aryl or nonexistent; with            the proviso that when A is nonexistent, B is nitrogen (N)            and B is bonded directly to the imide nitrogen.        -   B is sulfur or nitrogen with the proviso that when B is            sulfur only one of R₁ or R₂ is present;        -   X is an anionic counter ion;            -   wherein Q is selected from the group consisting of                acrylic acid and salts thereof, methacrylic acid and                salts thereof, maleic acid and salts thereof, maleic                anhydride, acrylamide, crotonic acid,                acrylamidomethylpropane sulfonic acid and salts thereof;            -   wherein W is selected from the group consisting of:                acrylic acid and salts thereof, methacrylic acid and                salts thereof, itaconic acid and salts thereof, maleic                acid and salts thereof, maleic anhydride, crotonic acid                and salts thereof, acrylamide, methacrylamide, vinyl                sulfonic acid, styrene sulfonate, N-tertbutylacrylamide,                N-isopropylacrylamide, butoxymethylacrylamide,                N,N-dimethylacrylamide, N,N-diethylacrylamide,                dimethylaminoethyl acrylate methyl chloride quaternary                salts, dimethylaminoethyl acrylate benzyl chloride                quaternary salts, dimethylaminoethyl acrylate methyl                sulfate quaternary salt, dimethylaminoethyl methacrylate                methyl sulfate quaternary salt, dimethylaminoethyl                acrylamide methyl sulfate quaternary salts,                dimethylaminopropyl acrylamide methyl sulfate quaternary                salts, dimethylaminopropyl methacrylamide methyl sulfate                quaternary salts, diallyldimethyl ammonium chloride,                N-vinyl formamide, dimethylamino ethyl methacrylate acid                salts (including, but not limited to, sulfuric acid and                hydrochloride acid salts), dimethylaminoethyl                methacrylate methyl chloride quaternary salt,                dimethylaminoethyl methacrylate benzyl chloride                quaternary salt, methacrylamidopropyl trimethyl ammonium                chloride, acrylamidopropyl trimethyl ammonium chloride,                methylene bis acrylamide, diallylamine, acid salts of                diallylamine, triallylamine, acid salts of                triallylamine, ethylene glycol dimethacrylate,                hydroxymethylacrylate, hydroxyethylacrylate,                hydroxypropylacrylate, hydroxypropylmethacrylate,                diethylene glycol dimethacrylate, triethylene glycol                dimethylacrylate, polyethylene glycol dimethacrylate,                glycidyl methacrylate, acrylamidomethylpropane sulfonic                acid and the sodium salt thereof, vinyl alcohol, vinyl                acetate, and N-vinylpyrrolidone;

    -   with the proviso that Q and W cannot both be the same;        -   wherein a is from about 0.001 to about 10.0 mole percent;        -   wherein j is from about 0 to about 99.999 mole percent;        -   wherein t is from about 0 to about 99.999 mole percent; and            wherein a+j+t=100;            G_(a) Q_(v) W_(f) S_(c)  (2)        -   wherein G is as previously defined;        -   wherein Q is as previously defined;        -   wherein W is as previously defined, with the proviso that Q            and W cannot both be the same;        -   wherein S is selected from the group consisting of            sulfomethylacrylamide and sulfoethylacrylamide;        -   wherein a is from about 0.001 to about 10.00 mole percent;        -   wherein v is from about 0 to about 97.999 mole percent;        -   wherein f is from about 1 to about 97.999 mole percent;        -   wherein c is from about 1 to about 40 mole percent; and            wherein a+v+f+c=100;        -   ii) using a fluorometer to detect the fluorescent signal of            said tagged treatment polymer;        -   iii) converting the fluorescent signal of said tagged            treatment polymer to the concentration of said tagged            treatment polymer; and        -   iv) adjusting the concentration of said tagged treatment            polymer according to what the desired concentration is for            said tagged treatment polymer in said industrial water            system.

    -   31. A tagged treatment polymer of claim 30 wherein Q is acrylic        acid and W is acrylamide.

    -   32. A tagged treatment polymer of claim 30 wherein Q is        acrylamide, W is acrylic acid and S is N-sulfomethylacrylamide.

    -   33. A tagged treatment polymer of claim 30 wherein Q is acrylic        acid and W is acrylamidomethylpropane sulfonic acid.

    -   34. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   35. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   36. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.

    -   37. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   38. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.

    -   39. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.

    -   40. A tagged treatment polymer of claim 30 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt and Q is acrylic acid.

    -   41. A method for maintaining the desired amount of tagged        treatment polymer in an industrial water system comprising the        steps of:

    -   a) adding an inert tracer and a tagged treatment polymer to the        water of an industrial water system, wherein said tagged        treatment polymer is selected from the group consisting of:        G_(a)Q_(j)W_(t)  (1)        -   wherein G is selected from the group consisting of:

    -   wherein G is selected from the group consisting of:

-   -   wherein Y is one or more of the following: H, F, Cl, Br, NO₂,        CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its salts,        SO₂NH₂ or SO₂NR₂;    -   Z is one of the following: CH₂, C═O, CR₂,NH, NR, NH₂ ⁺, NR₂ ⁺,        NOH, O, S, SO, or SO₂;    -   R₁ and R₂ are alkyl    -   R₃ is selected from the group consisting of allyl,        2-hydroxy-3-allyloxy-propyl, vinyl benzyl,        3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl and        2-methacryloxyethyl.    -   A is selected from the group consisting of alkyl, alkyloxyalkyl,        alkylamidoalkyl, aryl or nonexistent; with the proviso that when        A is nonexistent, B is nitrogen (N) and B is bonded directly to        the imide nitrogen.    -   B is sulfur or nitrogen with the proviso that when B is sulfur        only one of R₁ or R₂ is present;    -   X is an anionic counter ion;        -   wherein Q is selected from the group consisting of acrylic            acid and salts thereof, methacrylic acid and salts thereof,            maleic acid and salts thereof, maleic anhydride, acrylamide,            crotonic acid, acrylamidomethylpropane sulfonic acid and            salts thereof;        -   wherein W is selected from the group consisting of:            acrylic acid and salts thereof, methacrylic acid and salts            thereof, itaconic acid and salts thereof, maleic acid and            salts thereof, maleic anhydride, crotonic acid and salts            thereof, acrylamide, methacrylamide, vinyl sulfonic acid,            styrene sulfonate, N-tertbutylacrylamide,            N-isopropylacrylamide, butoxymethylacrylamide,            N,N-dimethylacrylamide, N,N-diethylacrylamide,            dimethylaminoethyl acrylate methyl chloride quaternary            salts, dimethylaminoethyl acrylate benzyl chloride            quaternary salts, dimethylaminoethyl acrylate methyl sulfate            quaternary salt, dimethylaminoethyl methacrylate methyl            sulfate quaternary salt, dimethylaminoethyl acrylamide            methyl sulfate quaternary salts, dimethylaminopropyl            acrylamide methyl sulfate quaternary salts,            dimethylaminopropyl methacrylamide methyl sulfate quaternary            salts, diallyldimethyl ammonium chloride, N-vinyl formamide,            dimethylamino ethyl methacrylate acid salts (including, but            not limited to, sulfuric acid and hydrochloride acid salts),            dimethylaminoethyl methacrylate methyl chloride quaternary            salt, dimethylaminoethyl methacrylate benzyl chloride            quaternary salt, methacrylamidopropyl trimethyl ammonium            chloride, acrylamidopropyl trimethyl ammonium chloride,            methylene bis acrylamide, diallylamine, acid salts of            diallylamine, triallylamine, acid salts of triallylamine,            ethylene glycol dimethacrylate, hydroxymethylacrylate,            hydroxyethylacrylate, hydroxypropylacrylate,            hydroxypropylmethacrylate, diethylene glycol dimethacrylate,            triethylene glycol dimethylacrylate, polyethylene glycol            dimethacrylate, glycidyl methacrylate,            acrylamidomethylpropane sulfonic acid and the sodium salt            thereof, vinyl alcohol, vinyl acetate, and            N-vinylpyrrolidone;    -   with the proviso that Q and W cannot both be the same;        -   wherein a is from about 0.001 to about 10.0 mole percent;        -   wherein j is from about 0 to about 99.999 mole percent;        -   wherein t is from about 0 to about 99.999 mole percent; and        -   wherein a+j+t=100;            G_(a) Q_(v) W_(f) S_(c)  (2)        -   wherein G is as previously defined;        -   wherein Q is as previously defined;        -   wherein W is as previously defined, with the proviso that Q            and W cannot both be the same;        -   wherein S is selected from the group consisting of            sulfomethylacrylamide and sulfoethylacrylamide;        -   wherein a is from about 0.001 to about 10.00 mole percent;        -   wherein v is from about 0 to about 97.999 mole percent;        -   wherein f is from about 1 to about 97.999 mole percent;        -   wherein c is from about 1 to about 40 mole percent; and        -   wherein a+v+f+c=100;        -   such that a desired concentration of said tagged treatment            polymer is present in said water;        -   b) using a fluorometer to detect the fluorescent signals of            said inert tracer and said tagged treatment polymer;        -   c) converting the fluorescent signals of said inert tracer            and said tagged treatment polymer to the concentration of            said inert tracer and said tagged treatment polymer; and        -   d) adjusting the concentration of said tagged treatment            polymer according to what the desired concentration is for            said tagged treatment polymer in said industrial water            system.    -   42. A tagged treatment polymer of claim 41 wherein Q is acrylic        acid and W is acrylamide.    -   43. A tagged treatment polymer of claim 41 wherein Q is        acrylamide, W is acrylic acid and S is N-sulfomethylacrylamide.    -   44. A tagged treatment polymer of claim 41 wherein Q is acrylic        acid and W is acrylamidomethylpropane sulfonic acid.    -   45. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.    -   46. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.    -   47. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamide and S is N        sulfomethylacrylamide.    -   48. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.    -   49. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride        quaternary salt, Q is acrylic acid, W is acrylamidomethylpropane        sulfonic acid.    -   50. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l)        xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt,        Q is acrylic acid, W is acrylamidomethylpropane sulfonic acid.    -   51. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl        quaternary salt and Q is acrylic acid.    -   52. A tagged treatment polymer of claim 41 wherein G is        sulfonated —N-(3-N′,N′-Dimethylaminopropyl) benzo ((k,l)        xanthene-3,4-dicarboxylic imide, vinylbenzyl chloride quaternary        salt and Q is acrylic acid.

EXAMPLES

The foregoing may be better understood by reference to the followingexamples, which is presented for purposes of illustration and is notintended to limit the scope of the invention.

Monomer Example 1

Preparation of Sulfonated —N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)xanthene-3,4-dicarboxylic imide, 2-Hydroxy-3-Allyloxypropyl Quat(S-NDMAPBXA-DCI-HAPQ) Benzoxanthene was synthesized according to themethod of A. T. Peters and Y. S. S. Behesti in The Journal of theSociety of Dyers and Colorists, 1989, 105, pages 29 to 35 and sulfonatedaccording to the procedure described by H. Troster U.S. Pat. No.3,888,863.

Step One:

Synthesis of Sulfonated —N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)xanthene-3,4-dicarboxylic imide (I)

A 25 ml round bottom flask was charged with sulfonated benzo (k,l)xanthene-3,4-dicarboxylic imide (0.5 g, 0.714 mmol, 64%), 6.5 mL waterand 0.15 g glacial acetic acid. 3-(dimethylamino)-1-propyl amine (0.131g, 1.28 mmol) was added dropwise. The mixture was refluxed for 5 hoursand cooled. The solution was concentrated to dryness to give theproduct.

Step 2:

Sulfonated —N-(3-N′,N′-Dimethylaminopropyl) Benzo (k,l)xanthene-3,4-dicarboxylic imide, 2-Hydroxy-3-Allyloxypropyl Quat(S-NDMAPBXA-DCI-HAPQ)

A 100 ml round bottom flask charged with I (2 g, 3.76 mmol) and 37.6 mLof water. Potassium carbonate (1.04 g, 7.52 mmol) and 0.52 g of allylglycidyl ether were added and the mix was heated to 50° C. for 2.5 hoursto form the product.

Polymer Example 1

Preparation of 0.2 mole % S-NDMAPBXA-DCI-HAPQ/80.9 mole % AcrylicAcid/18.9 mole % Acrylamidomethylpropane sulfonic acid

A reactor was charged with deionized water (93.6 g) andS-NDMAPBXA-DCI-HAPQ (prepared according to Monomer Example 1, 30.2 g,5.8 mmol) was heated to 65□C with stirring (750 rpm). At temperature,initiator solution 1 (2.3 g sodium persulfate in 6.8 g of deionizedwater), and initiator solution 2 (7.7 g sodium metabisulfite in 12.5 gof deionized water) were added separately at a constant flow rate over aperiod of 3.25 hours. Five minutes after initiator feed had started, amonomer solution 1 (8.2 g deionized water and 135.0 g, 1.875 mol ofacrylic acid), and monomer solution 2 (199.1 g, 0.51 mol of 58%Acrylamidomethylpropane sulfonic acid), were added separately at aconstant flow rate over a period of 3 hours. After 30 minutes, 50%sodium hydroxide (4.6 g, 0.058 mol) was added. After monomer andinitiator feeding was complete, the reaction was held at temperature foran additional 30 minutes.

Method of Use Example 1

Stability and Performance Testing:

The fluorescence properties (excitation and emission maxima) of polymersprepared using the monomers are given in Table I. Excitation maxima areall greater than 390 nm. The fluorescence of the monomers remainedinvariant over a pH range of approximately 2-12.

Another important feature of these polymers is the stability of thefluorescence in the presence of oxidizing biocides. The oxidizingbiocide stability test was performed in the following manner. Solutionsof simulated water were prepared with the desired levels of cations andanions at the desired pH. For these experiments the simulated coolingwater contained 150 ppm Ca (as CaCO₃), 75 ppm Mg (as CaCO₃) and 110 ppmalkalinity (as CaCO₃). The water was then adjusted to the desired pHwith HCl or NaOH. Tests were performed at pH 7 and 8. A series of threeamber bottles were labeled with the desired test sample. A 50 ml aliquotof the simulated water was delivered into each of the three labeledbottles. To one of the bottles (labeled “B”) was delivered 60 μl of a1200 ppm stock solution of bleach. To a second bottle (labeled “A”) wasdelivered 60 μl of a 1200 ppm stock solution of Acti-Brom® biocide,available from Nalco an Ecolab Company. To the third bottle (labeled“N”) was delivered 60 μl distilled water. The amount of free and totalchorine was measured immediately after the samples were prepared and 24hours later at the time of fluorescence analysis. The bottles werestored for 24 hours in the dark. The levels of free and total chlorinewere checked intermittently to ensure that there was a residual. After24 hours, fluorescence measurements were done using the sample marked“N” as the reference sample. The % fluorescence consumed (hereinafter “%Fl consumed”) in the presence of an oxidizing biocide was calculated asshown below. It is important to note that lower levels of % Fl Consumedindicate lower loss of fluorescent emission. Results for the fluorescentmonomers are given in Table I.

${\%\mspace{11mu} F\; 1\mspace{14mu}{Consumed}} = {\frac{{{Intensity}\mspace{14mu}{of}\mspace{14mu} N\mspace{14mu}{Sample}} - {{Intensity}\mspace{14mu}{of}\mspace{14mu} B\mspace{14mu}{or}\mspace{14mu} S\mspace{14mu}{Sample}}}{{Intensity}\mspace{14mu}{of}\mspace{14mu} N\mspace{11mu}{Sample}} \times 100}$

TABLE I Summary of Fluorescence Properties and OxidizingBiocide Stability of a Fluorescent Monomer Oxidizing Biocide StabilityEx- Monomer Fluorescence (% Fluorescence ample Name Properties Consumed)1 S-NDMAPBXA- Ex = 426 nm Bleach DCI-HAPQ Em = 475 nm (pH7) = 2.38% 2S-NDMAPBXA- Ex = 426 nm Acti-Brom® DCI-HAPQ Em = 475 nm (pH8) = 0.05%

When using the tagged treatment polymer as a compound of ascale-inhibitor product in an industrial water system, the only decreaseor loss of fluorescence signal from the polymer should be due to loss ofthe polymer under scaling conditions. When identifying a scaling eventas the reason for a loss of fluorescence, it is undesirable for thelevel of fluorescence to also vary based on pH changes, other componentspresent in the cooling water system, or from oxidizing biocides such asthe Acti-Brom® biocide system.

If the amount consumed by an oxidizing biocide is equal to or less than10% of the signal, then the tagged treatment polymer can be used in anindustrial water system. Although a small amount of the tagged treatmentpolymer is consumed in the presence of 2 ppm Acti-Brom® biocide, theresults given above indicate that the tagged treatment polymers aresufficiently stable to be used in industrial water systems whereActi-Brom® is present.

While this invention may be embodied in many different forms, theredescribed in detail herein specific preferred embodiments of theinvention. The present disclosure is an exemplification of theprinciples of the invention and is not intended to limit the inventionto the particular embodiments illustrated. All patents, patentapplications, scientific papers, and any other referenced materialsmentioned herein are incorporated by reference in their entirety.Furthermore, the invention encompasses any possible combination of someor all of the various embodiments described herein and/or incorporatedherein. In addition the invention encompasses any possible combinationthat also specifically excludes any one or more of the variousembodiments described herein and/or incorporated herein.

The above disclosure is intended to be illustrative and not exhaustive.This description will suggest many variations and alternatives to one ofordinary skill in this art. The compositions and methods disclosedherein may comprise, consist of, or consist essentially of the listedcomponents, or steps. As used herein the term “comprising” means“including, but not limited to”. As used herein the term “consistingessentially of” refers to a composition or method that includes thedisclosed components or steps, and any other components or steps that donot materially affect the novel and basic characteristics of thecompositions or methods. For example, compositions that consistessentially of listed ingredients do not contain additional ingredientsthat would affect the properties of those compositions. Those familiarwith the art may recognize other equivalents to the specific embodimentsdescribed herein which equivalents are also intended to be encompassedby the claims.

All ranges and parameters disclosed herein are understood to encompassany and all subranges subsumed therein, and every number between theendpoints. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more, (e.g. 1 to 6.1), and ending with amaximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), andfinally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 containedwithin the range.

All numeric values are herein assumed to be modified by the term“about,” whether or not explicitly indicated. The term “about” generallyrefers to a range of numbers that one of skill in the art would considerequivalent to the recited value (i.e., having the same function orresult). In many instances, the term “about” may include numbers thatare rounded to the nearest significant figure. Weight percent, percentby weight, % by weight, wt %, and the like are synonyms that refer tothe concentration of a substance as the weight of that substance dividedby the weight of the composition and multiplied by 100. Percentages andratios are by weight unless otherwise so stated.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contentclearly dictates otherwise. Thus, for example, reference to acomposition containing “a compound” includes a mixture of two or morecompounds. As used in this specification and the appended claims, theterm “or” is generally employed in its sense including “and/or” unlessthe content clearly dictates otherwise.

This completes the description of the preferred and alternateembodiments of the invention. Those skilled in the art may recognizeother equivalents to the specific embodiment described herein whichequivalents are intended to be encompassed by the claims attachedhereto.

What is claimed is:
 1. A tagged treatment polymer, the polymercomprising a chain of chemically bonded monomeric units, at least someof the monomeric units selected from the group consisting ofG_(a)Q_(j)W_(t), G_(a) Q_(v) W_(f) S_(c), and any combination thereof;wherein: the distribution of G, Q, W and S along the polymer chain arein random order and in relative amounts of a, j, t, v, f, and c; forpolymer G_(a) Q_(v) W_(f) S_(c) a is from about 0.001 to about 10.00mole percent; v is from about 0 to about 97.999 mole percent; f is fromabout 1 to about 97.999 mole percent; c is from about 1 to about 40 molepercent; and the sum of a, v, f, and c is 100; for polymerG_(a)Q_(j)W_(t) a is from about 0.001 to about 10.0 mole percent; j isfrom about 0 to about 99.999 mole percent; t is from about 0 to about99.999 mole percent; and the sum of a, j, and t is 100; G is selectedfrom Formula I or Formula II,

in Formula I, each Y is selected from NO₂, CO₂H and its salts, PO₃H₂ andit salts, SO₃H and its salts, SO₂NH₂ or SO₂NR₁R₂; Z is one of thefollowing: CH₂, C═O, CR₁R₂, NH, NR₁, NH₂ ⁺, NR₁R₂ ⁺, NOH, O, S, SO, orSO₂; R₃ is selected from allyl, 2-hydroxy-3-allyloxy-propyl, vinylbenzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl, or2-methacryloxyethyl; A is absent or selected from alkyl, alkyloxyalkyl,alkylamidoalkyl, or aryl, with the proviso that when A is absent, B isnitrogen (N) and B is bonded directly to the imide nitrogen; B is sulfuror nitrogen with the proviso that when B is sulfur only one of R₁ or R₂is present; X is an anionic counter ion; and in Formula II, each Y isselected from NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and itssalts, SO₂NH₂ or SO₂NR₁R₂; Z is selected from CH₂, C═O, CR₂, NH, NR₁,NH₂ ⁺, NR₁R₂ ⁺, NOH, O, S, SO, or SO₂; A is absent or selected fromalkyl, alkyloxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, or aryl;R₄ is selected from allyl, acryl, methacryl,2-hydroxy-3-allyloxy-propyl, vinyl benzyl, 2-acryloxyethyl or2-methacryloxyethyl; R₁ and R₂ are independently alkyl; Q is selectedfrom acrylic acid and salts thereof, methacrylic acid and salts thereof,maleic acid and salts thereof, maleic anhydride, acrylamide, crotonicacid, or acrylamidomethylpropane sulfonic acid and salts thereof; and Qcannot be the same as W; W is selected from acrylic acid and saltsthereof, methacrylic acid and salts thereof, itaconic acid and saltsthereof, maleic acid and salts thereof, maleic anhydride, crotonic acidand salts thereof, acrylamide, methacrylamide, vinyl sulfonic acid,styrene sulfonate, N-tertbutylacrylamide, N-i sopropylacrylamide,butoxymethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide,dimethylaminoethyl acrylate methyl chloride quaternary salts,dimethylaminoethyl acrylate benzyl chloride quaternary salts,dimethylaminoethyl acrylate methyl sulfate quaternary salt,dimethylaminoethyl methacrylate methyl sulfate quaternary salt,dimethylaminoethyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl acrylamide methyl sulfate quaternary salts,dimethylaminopropyl methacrylamide methyl sulfate quaternary salts,diallyldimethyl ammonium chloride, N-vinyl formamide, dimethylaminoethyl methacrylate acid salts (including, but not limited to, sulfuricacid and hydrochloride acid salts), dimethylaminoethyl methacrylatemethyl chloride quaternary salt, dimethylaminoethyl methacrylate benzylchloride quaternary salt, methacrylamidopropyl trimethyl ammoniumchloride, acrylamidopropyl trimethyl ammonium chloride, methylene bisacrylamide, diallylamine, acid salts of diallylamine, triallylamine,acid salts of triallylamine, ethylene glycol dimethacrylate,hydroxymethylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,hydroxypropylmethacrylate, diethylene glycol dimethacrylate, triethyleneglycol dimethylacrylate, polyethylene glycol dimethacrylate, glycidylmethacrylate, acrylamidomethylpropane sulfonic acid and the sodium saltthereof, vinyl alcohol, vinyl acetate, or N-vinylpyrrolidone; and S isselected from the group consisting of sulfomethylacrylamide andsulfoethylacrylamide.
 2. The polymer of claim 1, wherein G is selectedfrom the group consisting of sulfonated-N-(3-N′, N′-Dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropylquaternary salt and sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo(k,l) xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride quaternarysalt, Q is acrylic acid, W is acrylamide and S is Nsulfomethylacrylamide.
 3. The polymer of claim 1, wherein G is selectedfrom the group consisting of sulfonated-N-(3-N′, N′-Dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropylquaternary salt and sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo(k,l) xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt, Qis acrylic acid, W is acrylamide and S is N-sulfomethylacrylamide. 4.The polymer of claim 1, wherein G is sulfonated-N-(3-N′,N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W isacrylamide and S is N-sulfomethylacrylamide.
 5. The polymer of claim 1,wherein G is selected from the group consisting of sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt and sulfonated-N-(3-N′,N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt, Q is acrylic acid, W isacrylamidomethylpropane sulfonic acid.
 6. The polymer of claim 1,wherein G is selected from the group consisting of sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,2-hydroxy-3-allyloxypropyl quaternary salt and sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,vinyl benzyl chloride quaternary salt, Q is acrylic acid, W isacrylamidomethylpropane sulfonic acid.
 7. The polymer of claim 1,wherein G is sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt, Q isacrylic acid, and W is acrylamidomethylpropane sulfonic acid.
 8. Thepolymer of claim 1, wherein G is sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,vinylbenzyl chloride quaternary salt and Q is acrylic acid.
 9. Thepolymer of claim 1, wherein G is selected from the group consisting ofsulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt andsulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropyl quaternarysalt, and Q is acrylic acid.
 10. The polymer of claim 1, wherein G isselected from the group consisting of sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt and sulfonated-N-(3-N′,N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt, and Q is acrylic acid.
 11. Thepolymer of claim 1, wherein t is from about 0.001 to about 99.998%. 12.The polymer of claim 1, wherein Q is acrylic acid and W is acrylamide oracrylamidomethylpropane sulfonic acid.
 13. The polymer of claim 1,wherein Q is acrylamide, W is acrylic acid, and S isN-sulfomethylacrylamide.
 14. A fluorescent monomer selected from thegroup consisting of a compound of Formula I and a compound of FormulaII, wherein:

in Formula I, Y is selected from NO₂, CO₂H and its salts, PO₃H₂ and itsalts, SO₃H and its salts, SO₂NH₂ or SO₂NR₁R₂; Z is one of thefollowing: CH₂, C═O, CR₂, NH, NR₁, NH₂ ⁺, NR₁R₂ ⁺, NOH, O, S, SO, orSO₂; R₃ is selected from allyl, 2-hydroxy-3-allyloxy-propyl, vinylbenzyl, 3-methacrylamidopropyl, 3-acrylamidopropyl, 2-acryloxyethyl or2-methacryloxyethyl; A is absent or selected from alkyl, alkyloxyalkyl,alkylamidoalkyl, or aryl; with the proviso that when A is absent, B isnitrogen (N) and B is bonded directly to the imide nitrogen; B is sulfuror nitrogen with the proviso that when B is sulfur only one of R₁ or R₂is present; X is an anionic counter ion; in Formula II, Y is selectedfrom NO₂, CO₂H and its salts, PO₃H₂ and it salts, SO₃H and its salts,SO₂NH₂ or SO₂NR₂; Z is one of the following: CH₂, C═O, CR₂, NH, NR₁, NH₂⁺, NR₁R₂ ⁺, NOH, O, S, SO, or SO₂; A is absent or selected from alkyl,alkyloxyalkyl, alkoxy, alkylamidoalkyl, alkylamino, NH, or aryl; R₄ isselected from allyl, acryl, methacryl, 2-hydroxy-3-allyloxy-propyl,vinyl benzyl, 2-acryloxyethyl or 2-methacryloxyethyl; and R₁ and R₂ areindependently alkyl.
 15. The fluorescent monomer of claim 14, whereinthe fluorescent monomer is sulfonated-N-(3-N′, N′-Dimethylaminopropyl)benzo (k,l) xanthene-3,4-dicarboxylic imide, 2-hydroxy-3-allyloxypropylquaternary salt.
 16. The fluorescent monomer of claim 14, wherein thefluorescent monomer is sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo(k,l) xanthene-3,4-dicarboxylic imide, vinyl benzyl chloride quaternarysalt.
 17. The fluorescent monomer of claim 14, wherein the fluorescentmonomer is sulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, allyl chloride quaternary salt.
 18. Thefluorescent monomer of claim 14, wherein the fluorescent monomer issulfonated-N-(3-N′, N′-Dimethylaminopropyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt.19. The fluorescent monomer of claim 14, wherein the fluorescent monomeris sulfonated-N-(3-N′, N′-Dimethylaminoethyl) benzo (k,l)xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt.20. A fluorescent monomer selected from sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,2-hydroxy-3-allyloxypropyl quaternary salt; sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,vinyl benzyl chloride quaternary salt; sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,allyl chloride quaternary salt; sulfonated-N-(3-N′,N′-Dimethylaminopropyl) benzo (k,l) xanthene-3,4-dicarboxylic imide,3-methacrylamidopropyl quaternary salt; and sulfonated-N-(3-N′,N′-Dimethylaminoethyl) benzo (k,l) xanthene-3,4-dicarboxylic imide, 3-methacrylamidopropyl quaternary salt.